Benzopyrone compounds, preparation method and use thereof

ABSTRACT

The invention relates to pesticide and bactericide, specifically to the benzopyrone compounds and its preparation method and use thereof. The benzopyrone compounds of the invention having general formula (I): 
                         
The present invention, having good pesticide activity and broad bactericide activity, applied for controlling various pests in plants such as army worm, diamond backmoth and aphid, carmine spider mite, two-spotted spider mite, ladybeetle, mites and mosquito larvae. Various disease in plants can be controlled by the invention and that of grape downy mildew, rice sheath and culm blight, rice blast, tomato early blight, tomato late blight, wheat leaf rust, wheat leaf blotch, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber grey mold and so on.

FIELD OF THE INVENTION

The invention relates to insecticides and fungicides, specifically to benzopyrone compounds and its preparation method and use thereof.

BACKGROUND OF THE INVENTION

Benzopyrone and strobilurin (methoxyacrylate) compounds are natural products and known with biological active. Compounds of the following general formula have ever been published in JP04-182461:

The structure of compound JP51 in JP04-182461 is as follows:

Biological active data of the compound in JP04-182461 have not been disclosed. After synthesis and the biological evaluation, it was found that compound JP51 has low biological active.

SUMMARY OF THE INVENTION

The aim of the present invention is to provide benzopyrone compounds with biological activity against all sorts of plant diseases and insects at very low dosage, and the compounds can be applied in agriculture to control diseases and insects in plant.

Detailed description of the invention is as follows:

The present invention offered benzopyrone compounds having general formula (I):

wherein: A is selected from CH or N;

B is selected from O, S or NR₉; R₉ is selected from H or C₁-C₁₂alkyl;

R₁ and R₂ are respectively selected from H, C₁-C₁₂alkyl or C₁-C₁₂ haloalkyl;

R₃ is selected from H, C₁-C₁₂alkyl, C₁-C₁₂ haloalkyl or C₁-C₁₂ alkoxy;

R₄, R₅, R₆, R₇, and R₈ may be the same or different, selected from H, halo, CN, NO₂, C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₁-C₁₂haloalkyl, C₁-C₁₂alkoxy, C₁-C₁₂alkylthio, C₁-C₁₂alkylsulfonyl, C₁-C₁₂alkylcarbonyl, C₁-C₁₂alkoxyC₁-C₁₂alkyl, C₁-C₁₂alkoxycarbonyl, C₁-C₁₂alkoxycarbonyl C₁-C₁₂alkyl, C₁-C₁₂haloalkoxyC₁-C₁₂alkyl, or amino C₁-C₁₂alkyl in which amino is substituted with 0-2 C₁-C₁₂ alkyl, 0-3 substituted groups of aryl, aryloxyl, arylC₁-C₁₂alkyl, arylC₁-C₁₂alkoxy, aryloxyC₁-C₁₂alkyl, arylC₁-C₁₂alkoxylC₁-C₁₂alkyl, heteroaryl, heteroarylC₁-C₁₂alkyl, or heteroarylC₁-C₁₂alkoxyl, the 0-3 substituted groups may be selected from halo, NO₂, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆alkoxyC₁-C₆alkyl, and the groups having general formula are as follows:

wherein: R₁₀ and R₁₁ are selected from H, C₁-C₁₂alkyl, aryl or aryl C₁-C₁₂alkyl; when R₃, R₄, R₅, R₆, R₇, and R₈ are all H, B is not NR₉;

and stereoisomer.

The preferred compounds of general formula (I) of this invention are:

A is selected from CH or N;

B is selected from O, S or NR₉; R₉ is selected from H or C₁-C₆alkyl;

R₁ and R₂ are respectively selected from H, C₁-C₆alkyl or C₁-C₆ haloalkyl;

R₃ is selected from H, C₁-C₆alkyl, C₁-C₆ haloalkyl or C₁-C₆alkoxy;

R₄, R₅, R₆, R₇, and R₈ may be the same or different, selected from H, halo, CN, NO₂, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆ alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylcarbonyl, C₁-C₆ alkoxyC₁-C₆alkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxycarbonylC₁-C₆alkyl, C₁-C₆haloalkoxyC₁-C₆alkyl, or amino C₁-C₆alkyl in which amino is substituted with 0-2 C₁-C₁₂ alkyl, 0-3 substituted groups of aryl, aryloxyl, arylC₁-C₆alkyl, arylC₁-C₆alkoxy, aryloxyC₁-C₆alkyl, arylC₁-C₆alkoxylC₁-C₆alkyl, heteroaryl, heteroarylC₁-C₆alkyl, heteroarylC₁-C₆alkoxyl, the 0-3 substituted groups may be selected from halo, NO₂, C₁-C₂alkyl, C₁-C₂haloalkyl, C₁-C₂alkoxy or C₁-C₂alkoxyC₁-C₂alkyl, and groups having formula are as follows:

wherein: R₁₀ and R₁₁ are respectively selected from H, C₁-C₁₂alkyl, aryl or arylC₁-C₆alkyl; when R₃, R₄,R₅, R₆, R₇, R₈ are all H, B is not NR₉;

Further more, the preferred compounds of general formula (I) of this invention are:

A is selected from CH or N;

B is selected from O or NH;

R₁ and R₂ are respectively selected from methyl;

R₃ is selected from H or methyl;

R₄, R₅, R₆, R₇, and R₈ may be the same or different, respectively selected from H, halo, CN, NO₂, C₁-C₆alkyl, C₂-C₆ alkenyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆ alkoxyC₁-C₆alkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkoxycarbonylC₁-C₃alkyl, C₁-C₃haloalkoxyC₁-C₃alkyl, or amino C₁-C₃alkyl in which amino is substituted with 0-2 C₁-C₃ alkyl, phenyl, phenoxy, phenylC₁-C₂alkyl, phenylC₁-C₂alkoxy, phenoxyC₁-C₂alkyl, phenylmethyl, phenylmethoxyl, or phenylmethoxyC₁-C₂alkyl substituted with 0-2 halo, NO₂, C₁-C₂alkyl, C₁-C₂haloalkyl, C₁-C₂alkoxy or C₁-C₂alkoxyC₁-C₂alkyl, and the substituted group having general formula is as follows:

wherein: R₁₀ and R₁₁ are respectively selected from H or C₁-C₆alkyl; when R₃, R₄, R₅, R₆, R₇, and R₈ are all H, B is not NH.

Even more preferred compounds of formula (I) of this invention are:

A is selected from CH or N;

B is selected from O or NH;

R₁ and R₂ are selected from methyl;

R₃ is selected from H or methyl;

R₄, R₅, R₆, R₇, and R₈ may be the same or different, respectively selected from H, Cl, Br, F, CN, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, Cl -C₆alkoxy, C₁-C₆alkoxyC₁-C₃alkyl, C₁-C₃haloalkoxyC₁-C₃alkyl, amino C₁-C₃alkyl in which amino is substituted with 0-2 C₁-C₃ alkyl, phenyl, phenoxy, phenylmethyl, phenylmethoxyl, substituted with 0-2 halo, NO₂, C₁-C₂alkyl, C₁-C₂haloalkyl, C₁-C₂alkoxy or C₁-C₂alkoxyC₁-C₂alkyl, and the substituted groups having general formula is as follows:

wherein: R₁₀ and R₁₁ are selected from methyl; when R₃, R₄, R₅, R₆, R₇, R₈ are all H, B is not NH.

The following is the meaning of terms in the general formula (I):

Halogen or halo is meant to include fluoro, chloro, bromo or iodo.

The alkyl includes either straight or branched chain alkyl such as methyl, ethyl, propyl, isopropyl or tert-butyl.

The haloalkyl refers to straight or branched chain alkyl , in which hydrogen atom may be all or partly substituted with halogen, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, or trifluoromethyl.

The alkoxy refers to straight or branched chain alkyl, which is linked to the structure by oxygen atom.

The haloalkoxy refers to straight or branched chain alkoxy, in which hydrogen atom may be all or partly substituted with halogen_, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, or trifluoroethoxy.

The alkenyl refers to an straight or branched, having double bonds at any position such as vinyl allyl. Substituted alkenyl includes arylvinyl which is substituted at any position with any group.

The alkynyl refers to straight or branched, having triple bonds at any position. such as ethynyl, propynyl. Substituted alkynyl includes arylethynyl which is substituted at any position with any group.

The aryl and aryl in arylalkyl, arylalkenyl, arylalkynyl, aryloxy, aryloxyalkyl include phenyl and naphthyl.

The substituent group in phenyl, phenoxy, phenylmethyl, phenylmethoxy are H, alkyl, alkoxy, haloalkyl, haloalkoxy, halo, NO₂, CN and the like. The number of the substituent group can be from one to five.

The hetero aryl in this invention refers to five member ring or six member ring containing one or many N, O, S hetero atom such as furan, thiophene, pyrrole, pyrazole, imidazole, thiazole, triazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, benzofuran.

Because of the C═C and C═N link to different substituted group, the compounds of the invention may form geometrical isomer (the different isomers are respectively expressed with Z and E). Z isomer and E isomer and their mixture in any proportion are included in the invention.

The present invention is explained by the compounds of the following table I, but without being restricted thereby.

As provided in table 1, where R₁, R₂═CH₃; P is C(CH₃)═NOCH₃; M is C₆H₃-3, 4-(OCH₃)₂.

TABLE 1 Physical- No. A B R₃ R₄ R₅ R₆ R₇ R₈ property* 1 CH O H H H H H H oil 2 CH O H H CH₃ H H H 140~143 3 CH O H H CH₃ H H CH₃ 188–190 4 CH O H H C₆H₅ H H CH₃ 146–148 5 CH O H CH₃ CH₃ H H H 120~122 6 CH O H CH₃ CH₃ H H CH₃ 174~176 7 CH O H H CF₃ H H H 164~166 8 CH O H H CH₃ H H P oil 9 CH O H H CH₃ H P H 183~185 10 CH O H H CH₃ H COCH₃ H 169~172 11 CH O H H CH₃ H H COCH₃ 165~167 12 CH O H Cl CH₃ H H H 162–164 13 CH O H H CH₂Cl H H H 14 CH O H Cl CH₂Cl H H H 15 CH O H Cl CH₂OCH₃ H H H 16 CH O H Cl CH₂CH₃ H H H 17 CH O H H CH₂CH₃ H H CH₃ 154–156 18 CH O H C₂H₅ CH₃ H H H 132–135 19 CH O H H CH₂OCH₃ H H H 140–142 20 CH O H H CH₂OC₂H₅ H H H 21 CH O H Cl CH₂OC₂H₅ H H H 22 CH O H OCH₃ CH₂OCH₃ H H H 23 CH O H N(CH₃)₂ CH₃ H H H 24 CH O H CN H H H H 166–168 25 CH O H Cl CH₃ H H CH₃ 202–204 26 CH O H H CH(CH₃)₂ H H H 128–130 27 CH O H C₃H₇ CH₃ H H H 142–144 28 CH O H H tC₄H₉ H H H 29 CH O H H 4-Cl—C₆H₄ H H H 149–152 30 CH O H Cl 4-Cl—C₆H₄ H H H 31 CH O H H 4-Cl—C₆H₄ H H CH₃ 32 CH O H Cl C₆H₅ H H H 142–144 33 CH O H H CH₂CH₃ H H H 134–136 34 CH O H H CH₂C₂H₅ H H H 118–120 35 CH O H H CH₂C₂H₅ H H CH₃ 146–148 36 CH O H Cl CH₂C₂H₅ H H H 118–120 37 CH O H CH₃ CH₂C₂H₅ H H H 112–115 38 CH O H H 4-F—C₆H₄ H H H 132–134 39 CH O H Cl 4-F—C₆H₄ H H H 40 CH O H H 4-F—C₆H₄ H H CH₃ 41 CH O H H 4-CF₃—C₆H₄ H H H 161–162 42 CH O H Cl 4-CF₃—C₆H₄ H H H 43 CH O H Cl CH₂N(CH₃)₂ H H H 44 CH O H OCH₃ C₂H₅ H H H 45 CH O H OCH₃ CH₃ H H H 46 CH O H OC₂H₅ CH₃ H H H 47 CH O H H CH₂OCH₂CF₃ H H H 48 CH O H Cl CH₂OCH₂CF₃ H H H 49 CH O H F CF₃ H H H 50 CH O H F CH₃ H H H 163–164 51 CH O H H CH₂N(CH₃)₂ H H H 52 CH O H H C₆H₅ H H H 130–133 53 CH O H Cl Cl H H H 54 CH O H F Cl H H H 55 CH O H H CH₂OCH₂C₆H₅ H P H 56 CH O H OCH₃ 4-Cl—C₆H₅ H H H 57 CH O H F 4-Cl—C₆H₅ H H H 58 CH O H H M H H H 81–83 59 CH O H Cl M H H H 60 CH O H Cl M H H CH₃ 61 CH O H CH₃S CH₃ H H H 62 CH O H CH₃SO₂ CH₃ H H H 63 CH O H F F H H H 64 CH O H CH₃SO₂ Cl H H H 65 CH O H H 4-NO₂—C₆H₅ H H H 66 CH O H Cl 4-NO₂—C₆H₅ H H H 67 CH O H H 4-NO₂—C₆H₅ H H CH₃ 68 CH O H PhCH₂ CH₃ H H H 159–162 69 CH O H PhCH₂ CH₃ H H CH₃ 70 CH O H CF₃CH₂O C₃H₇ H H H 71 CH NH H CH₃ CH₃ H H H 72 CH NH H CH₃ CH₃ H H CH₃ 73 CH NH H OCH₃ CF₃ CH₃ H H 74 CH NH H OCH₃ CH₃ F H P 75 CH NH H H CF₃ H H CH₃ 76 CH NH H CH₃ CH₂Cl H H H 77 CH NH H CH₃ CH₂Cl H H CH₃ 78 CH NH H Cl CH₂Cl H H H 79 CH NH H H M Cl H P 80 CH NH H H M H P H 81 CH NH H H M H COCH₃ H 82 CH NH H H M H H COCH₃ 83 CH NH H Cl CH₂OCH₃ H H H 84 CH NH H H 4-C₆H₅Cl H H H 85 CH NH H H 4-C₆H₅Cl H H CH₃ 86 CH NH H H CH₂OCH₃ H H CH₃ 87 CH NH H CH₃ CH₂OCH₃ H H H 88 CH NH H CH₃ CH₂OCH₃ H H CH₃ 89 CH NH H H CH₂OCH₃ H H H 90 CH NH H H CH₂OCH₃ H H P 91 CH NH H H CH₂OCH₂CF₃ H P H 92 CH NH H H CH₂N(CH₃)₂ H H H 93 CH NH H H CH₂OCH₂CF₃ H H COCH₃ 94 CH NH H Cl CH₂OC₂H₅ H H H 95 CH NH H H CH₂OC₂H₅ H H H 96 CH NH H H CH₂OC₂H₅ H H CH₃ 97 CH NH H H CF₃ H H CH₃ 98 CH NH H CH₃ CF₃ H H H 99 CH NH H CH₃ Cl H H CH₃ 100 N O H Cl CH₃ H H H 172–174 101 N O H H CH₃ H H H 150~152 102 N O H H CH₃ H H CH₃ 178–180 103 N O H CH₃ CH₃ H H H 112~118 104 N O H F CH₃ H H H 105 N O H H CF₃ H H Cl 106 N O H CH₃ CH₃ H H CH₃ 184~186 107 N O H H CH₃ H P CO₂CH₃ 108 N O H H CH₃ H COCH₃ CO₂CH₃ 109 N O H Cl CH₃ H H CH₃ 198–200 110 N O H H CH₂Cl H H CO₂CH₃ 111 N O H H H H H H 106~110 112 N O H H CH₂Cl H H CF₃ 113 N O H H 3-CF₃—C₆H₄ H H CF₃ 114 N O H CH₃ 3-CH₃—C₆H₄ H H CF₃ 115 N O H CH₃ 4-CH₃—C₆H₄ H H CF₃ 116 N O H H CH₂Cl H H H 117 N O H Cl CH₂Cl H H H 118 N O H Cl CH₂F H H H 119 N O H H CH₂F H H H 120 N O H H CH₂Br H H H 121 N O H H CH₂OCH₃ H H CH₂N(CH₃)₂ 122 N O H Cl CH₂OCH₃ H H CH₂N(CH₃)₂ 123 N O H CH₃ CH₂OCH₃ H H CH₂N(CH₃)₂ 124 N O H H CH₂OCH₃ H H F 125 N O H CH₃ CH₂OCH₃ H H F 126 N O H CH₃ CH₂OCH₃ H CO₂CH₃ CH₂N(CH₃)₂ 127 N O H H CH₂OCH₃ H H H 128 N O H H CH₂OCH₃ H H P 129 N O H H 3-CF₃—C₆H₄ H P H 130 N O H H 3-CH₃—C₆H₄ H COCH₃ H 131 N O H H 4-CH₃—C₆H₄ H H COCH₃ 132 N O H Cl CH₂OC₂H₅ H H H 133 N O H H CH₂OC₂H₅ H H H 134 N O H H CH₂OC₂H₅ H H CH₃ 135 N O H H 3-OCH₃—C₆H₄ H H CH₃ 136 N O H CH₃ 4-OCH₃—C₆H₄ H H H 137 N O H CH₃ 2-OCH₃—C₆H₄ H H CH₃ 138 N O H H CH₂OC₂H₅ H H Cl 139 N O H H CH₂OC₂H₅ H H P 140 N O H H M H P H 141 N O H H 3-CF₃—C₆H₄ H COCH₃ H 142 N O H H 3-CH₃—C₆H₄ H H COCH₃ 143 N O H H 4-CH₃—C₆H₄ H H H 144 N O H H 2-Cl—C₆H₄ H H H 145 N O H H 3-Cl—C₆H₄ H H CH₃ 146 N O H H CH₂OCH₂CF₃ H H CH₃ 147 N O H CH₃ CH₂OCH₂CF₃ H H H 148 N O H CH₃ —CH₂OC₆H₅ H H CH₃ 149 N O H H —CH₂OC₆H₅ H H H 150 N O H H CH₂OCH₂C₆H₅ H H P 151 N O H H CH₂OCH₂C₆H₅ H P H 152 N O H H 4-Cl—C₆H₄ H COCH₃ H 153 N NH H H CH₃ H H H 210–214 154 N NH H CH₃ CH₃ H H CH₃ 178~180 155 N NH H H 2-Cl—C₆H₄ H H CH₃ 156 N NH H CH₃ 3-Cl—C₆H₄ H H H 157 N NH H CH₃ 4-Cl—C₆H₄ H H CH₃ 158 N NH H Cl CH₂Cl H H H 159 N NH H Cl CH₃ H H H 160 N NH H H 3-CF₃—C₆H₄ H P H 161 N NH H H 3-CH₃—C₆H₄ H COCH₃ H 162 N NH H H 4-CH₃—C₆H₄ H H COCH₃ 163 N NH H H CH₂OCH₃ H H H 164 N NH H H 4-F—C₆H₄ H H H 165 N NH H H 2-F—C₆H₄ H H CH₃ 166 N NH H H C₆H₃-3,5(Cl)₂ H H CH₃ 167 N NH H CH₃ 2-OCH₃—C₆H₄ H H H 168 N NH H CH₃ 2-OCH₃—C₆H₄ H H CH₃ 169 N NH H Cl CH₂OCH₃ H H H 170 N NH H H CH₂OCH₃ H H P 171 N NH H H 3,5(Cl)₂—C₆H₃ H P H 172 N NH H H 2,4(Cl)₂—C₆H₃ H H H 173 N NH H H 3,4(Cl)₂—C₆H₃ H H H 174 N NH H Cl CH₂OC₂H₅ H H H 175 N NH H H CH₂OC₂H₅ H H H 176 N NH H H CH₂OC₂H₅ H H CH₃ 177 N NH H H CF₃ H H CH₃ 178 N NH H CH₃ CF₃ H H H 179 N NH H CH₃ Cl H H CH₃ 180 N NH H H Cl H H H 181 N NH H H CH₃ H H Cl 182 N NH H H C₆H₅ H H Cl 183 N NH H CH₃ CH₃ H H F 184 N NH H CH₃ CH₃ H H H 185 N NH H H CF₃ H H Cl 186 N NH H CH₃ 4-F—C₆H₄ H H CH₃ 187 N NH H H 2-F—C₆H₄ H P CO₂CH₃ 188 N NH H H 2-Cl—C₆H₄ H COCH₃ CO₂CH₃ 189 N NH H H 3-Cl—C₆H₄ H H CO₂CH₃ 190 N NH H H 4-Cl—C₆H₄ H H CO₂CH₃ 191 N NH H H CH₂Cl H CH₃ H 192 N NH H H CH₂Cl H CO₂C₂H₅ CF₃ 193 N NH H H CH₂Cl H H CF₃ 194 N NH H CH₃ M H CO₂C₂H₅ CF₃ 195 N NH H CH₃ CH₂Cl H H CF₃ 196 N NH H H CH₂Cl H H H 197 N NH H H CH₂Cl H H P 198 N NH H H CH₂Cl H P H 199 N NH H H CH₂Cl H COCH₃ H 200 N NH H CH₃ 3,5-diCl—C₆H₃ H CO₂CH₃ H 201 CH O CH₃ H H H H H 202 CH O CH₃ H CH₃ H H H 203 CH O CH₃ H CH₃ H H CH₃ 204 CH O CH₃ H C₆H₅ H H CH₃ 205 CH O CH₃ CH₃ CH₃ H H H 206 CH O CH₃ CH₃ CH₃ H H CH₃ 207 CH O CH₃ H CF₃ H H H 208 CH O CH₃ H CH₃ H H P 209 CH O CH₃ H CH₃ H P H 210 CH O CH₃ H CH₃ H COCH₃ H 211 CH O CH₃ H CH₃ H H COCH₃ 212 CH O CH₃ H CH₂Cl H H H 213 CH O CH₃ Cl CH₂Cl H H H 214 CH O CH₃ H CH₂Cl H H CF₃ 215 CH O CH₃ H CH₂Cl H H CH₃ 216 CH O CH₃ CH₃ CH₂OCH₃ H H H 217 CH O CH₃ CH₃ CH₂OCH₃ H H CH₃ 218 CH O CH₃ OCH₃ CH₂Cl H H H 219 CH O CH₃ H CH₂Cl H H P 220 CH O CH₃ H CH₂Cl H P H 221 CH O CH₃ H CH₂Cl H COCH₃ H 222 CH O CH₃ H CH₂Cl H H COCH3 223 CH O CH₃ H CH₂OCH₂CF₃ H H H 224 CH O CH₃ Cl CH₂OC₂H₅ H H H 225 CH O CH₃ Cl CH₂OCH₃ H H CH₃ 226 CH O CH₃ H CH₂OCH₃ H H CH₃ 227 CH O CH₃ CH₃ 3-CF₃—C₆H₄ H H H 228 CH O CH₃ CH₃ 3-CH₃—C₆H₄ H H CH₃ 229 CH O CH₃ H 4-CH₃—C₆H₄ H H H 230 CH O CH₃ H 2-Cl —C₆H₄ H H P 231 CH O CH₃ H 3-Cl —C₆H₄ H P H 232 CH O CH₃ H CF₃ H COCH₃ H 233 CH O CH₃ Cl CH₂OCH₃ H H COCH₃ 234 CH O CH₃ OCH₃ CH₂OC₂H₅ H H H 235 CH O CH₃ C₂H₅ CH₂OC₂H₅ H CH₃ H 236 CH O CH₃ H CH₂OC₂H₅ H H CH₃ 237 CH O CH₃ Cl CH₂OC₂H₅ H CO₂C₂H₅ CH₃ 238 CH O CH₃ CH₃ 2-F—C₆H₄ H H H 239 CH O CH₃ CH₃ 3-F—C₆H₄ H H CH₃ 240 CH O CH₃ H 4-F—C₆H₄ H H H 241 CH O CH₃ H CH₂OC₂H₅ H H P 242 CH O CH₃ H CH₂OC₂H₅ H P H 243 CH O CH₃ H CH₂OC₂H₅ H COCH₃ H 244 CH O CH₃ H CH₂OC₂H₅ H H COCH₃ 245 CH O CH₃ H CH₂OCH₂CF₃ H H H 246 CH O CH₃ Cl CH₂OCH₂CF₃ H H H 247 CH O CH₃ H CF₃ H H CH₃ 248 CH O CH₃ H CH₂OCH₂CF₃ H H CH₃ 249 CH O CH₃ CH₃ CH₂OCH₂CF₃ H H H 250 CH O CH₃ CH₃ —CH₂OPh H H CH₃ 251 CH O CH₃ H —CH₂OPh H H H 252 CH O CH₃ H CH₂OCH₂Ph H H P 253 CH O CH₃ H CH₂OCH₂Ph H P H 254 CH O CH₃ H 4-Cl—C₆H₅ H COCH₃ H 255 CH O CH₃ H 4-Cl—C₆H₅ H H COCH₃ 256 CH O CH₃ H M H CO₂C₂H₅ H 257 CH O CH₃ H M H H H 258 CH O CH₃ Cl M H H CH₃ 259 CH O CH₃ H M H H CH₃ 260 CH O CH₃ CH₃ M H H H 261 CH NH CH₃ Cl H H H H 262 CH NH CH₃ Cl CH₃ H H H 263 CH NH CH₃ H CH₃ H H CH₃ 264 CH NH CH₃ H C₆H₅ H H CH₃ 265 CH NH CH₃ CH₃ CH₃ H H H 266 CH NH CH₃ CH₃ CH₃ H H CH₃ 267 CH NH CH₃ OCH₃ CF₃ H H H 268 CH NH CH₃ OCH₃ CH₃ H H P 269 CH NH CH₃ H CH₃ H P H 270 CH NH CH₃ H CH₃ H COCH₃ H 271 CH NH CH₃ H CH₃ H H COCH₃ 272 CH NH CH₃ H CH₂Cl H H H 273 CH NH CH₃ H M H H H 274 CH NH CH₃ H CH₂Cl H H CH₃ 275 CH NH CH₃ H CF₃ H H CH₃ 276 CH NH CH₃ CH₃ CH₂Cl H H H 277 CH NH CH₃ CH₃ CH₂Cl H H CH₃ 278 CH NH CH₃ Cl CH₂Cl H H H 279 CH NH CH₃ H M H H P 280 CH NH CH₃ H M H P H 281 CH NH CH₃ H M H COCH₃ H 282 CH NH CH₃ H M H H COCH₃ 283 CH NH CH₃ Cl CH₂OCH₃ H H H 284 CH NH CH₃ H 4-C₆H₅Cl H H H 285 CH NH CH₃ H 4-C₆H₅Cl H H CH₃ 286 CH NH CH₃ H CH₂OCH₃ H H CH₃ 287 CH NH CH₃ CH₃ CH₂OCH₃ H H H 288 CH NH CH₃ CH₃ CH₂OCH₃ H H CH₃ 289 CH NH CH₃ H CH₂OCH₃ H H H 290 CH NH CH₃ H CH₂OCH₃ H H P 291 CH NH CH₃ H CH₂OCH₂CF₃ H P H 292 CH NH CH₃ H CH₂OCH₂CF₃ H COCH₃ H 293 CH NH CH₃ H CH₂OCH₂CF₃ H H COCH₃ 294 CH NH CH₃ Cl CH₂OC₂H₅ H H H 295 CH NH CH₃ H CH₂OC₂H₅ H H H 296 CH NH CH₃ H CH₂OC₂H₅ H H CH₃ 297 CH NH CH₃ H CF₃ H H CH₃ 298 CH NH CH₃ CH₃ CF₃ H H H 299 CH NH CH₃ CH₃ Cl H H CH₃ 300 CH NH CH₃ H Cl H H H 301 N O CH₃ H CH₃ H H H 302 N O CH₃ H C₆H₅ H H Cl 303 N O CH₃ CH₃ CH₃ H H H 304 N O CH₃ CH₃ CH₃ H H H 305 N O CH₃ H CF₃ H H Cl 306 N O CH₃ CH₃ CH₃ H H CH₃ 307 N O CH₃ H CH₃ H P CO₂CH₃ 308 N O CH₃ H CH₃ H COCH₃ CO₂CH₃ 309 N O CH₃ H CH₃ H H CO₂CH₃ 310 N O CH₃ H CH₂Cl H H CO₂CH₃ 311 N O CH₃ H H H H H 312 N O CH₃ H CH₂Cl H H CF₃ 313 N O CH₃ H 3-CF₃—C₆H₄ H H CF₃ 314 N O CH₃ CH₃ 3-CH₃—C₆H₄ H H CF₃ 315 N O CH₃ CH₃ 4-CH₃—C₆H₄ H H CF₃ 316 N O CH₃ H CH₂Cl H H H 317 N O CH₃ H CH₂Cl H H P 318 N O CH₃ H CH₂Cl H P H 319 N O CH₃ H CH₂Cl H COCH₃ H 320 N O CH₃ H CH₂Cl H H COCH3 321 N O CH₃ H CH₂OCH₃ H H CH₂N(CH₃)₂ 322 N O CH₃ Cl CH₂OCH₃ H H CH₂N(CH₃)₂ 323 N O CH₃ CH₃ CH₂OCH₃ H H CH₂N(CH₃)₂ 324 N O CH₃ H CH₂OCH₃ H H F 325 N O CH₃ CH₃ CH₂OCH₃ H H F 326 N O CH₃ CH₃ CH₂OCH₃ H CO₂CH₃ CH₂N(CH₃)₂ 327 N O CH₃ H CH₂OCH₃ H H H 328 N O CH₃ H CH₂OCH₃ H H P 329 N O CH₃ H 3-CF₃—C₆H₄ H P H 330 N O CH₃ H 3-CH₃—C₆H₄ H COCH₃ H 331 N O CH₃ H 4-CH₃—C₆H₄ H H COCH₃ 332 N O CH₃ Cl CH₂OC₂H₅ H H H 333 N O CH₃ H CH₂OC₂H₅ H H H 334 N O CH₃ H CH₂OC₂H₅ H H CH₃ 335 N O CH₃ H 3-OCH₃—C₆H₄ H H CH₃ 336 N O CH₃ CH₃ 4-OCH₃—C₆H₄ H H H 337 N O CH₃ CH₃ 2-OCH₃—C₆H₄ H H CH₃ 338 N O CH₃ H CH₂OC₂H₅ H H Cl 339 N O CH₃ H CH₂OC₂H₅ H H P 340 N O CH₃ H M H P H 341 N O CH₃ H 3-CF₃—C₆H₄ H COCH₃ H 342 N O CH₃ H 3-CH₃—C₆H₄ H H COCH₃ 343 N O CH₃ H 4-CH₃—C₆H₄ H H H 344 N O CH₃ H 2-Cl—C₆H₄ H H H 345 N O CH₃ H 3-Cl—C₆H₄ H H CH₃ 346 N O CH₃ H CH₂OCH₂CF₃ H H CH₃ 347 N O CH₃ CH₃ CH₂OCH₂CF₃ H H H 348 N O CH₃ CH₃ —CH₂OPh H H CH₃ 349 N O CH₃ H —CH₂OPh H H H 350 N O CH₃ H CH₂OCH₂Ph H H P 351 N O CH₃ H CH₂OCH₂Ph H P H 352 N O CH₃ H 4-Cl—C₆H₄ H COCH₃ H 353 N NH CH₃ H CH₃ H H H 354 N NH CH₃ CH₃ CH₃ H H CH₃ 355 N NH CH₃ H 2-Cl—C₆H₄ H H CH₃ 356 N NH CH₃ CH₃ 3-Cl—C₆H₄ H H H 357 N NH CH₃ CH₃ 4-Cl—C₆H₄ H H CH₃ 358 N NH CH₃ H CH₂Cl H H H 359 N NH CH₃ H M H H P 360 N NH CH₃ H 3-CF₃—C₆H₄ H P H 361 N NH CH₃ H 3-CH₃—C₆H₄ H COCH₃ H 362 N NH CH₃ H 4-CH₃—C₆H₄ H H COCH₃ 363 N NH CH₃ H CH₂OCH₃ H H H 364 N NH CH₃ H 4-F—C₆H₄ H H H 365 N NH CH₃ H 2-F—C₆H₄ H H CH₃ 366 N NH CH₃ H C₆H₃-3,5(Cl)₂ H H CH₃ 367 N NH CH₃ CH₃ 2-OCH₃—C₆H₄ H H H 368 N NH CH₃ CH₃ 2-OCH₃—C₆H₄ H H CH₃ 369 N NH CH₃ Cl CH₂OCH₃ H H H 370 N NH CH₃ H CH₂OCH₃ H H P 371 N NH CH₃ H C₆H₃-3,5(Cl)₂ H P H 372 N NH CH₃ H CH₂OCH₂CF₃ H COCH₃ H 373 N NH CH₃ H CH₂OCH₂CF₃ H H COCH₃ 374 N NH CH₃ Cl CH₂OC₂H₅ H H H 375 N NH CH₃ H CH₂OC₂H₅ H H H 376 N NH CH₃ H CH₂OC₂H₅ H H CH₃ 377 N NH CH₃ H CF₃ H H CH₃ 378 N NH CH₃ CH₃ CF₃ H H H 379 N NH CH₃ CH₃ Cl H H CH₃ 380 N NH CH₃ H Cl H H H 381 N NH CH₃ H CH₃ H H Cl 382 N NH CH₃ H C₆H₅ H H Cl 383 N NH CH₃ CH₃ CH₃ H H F 384 N NH CH₃ CH₃ CH₃ H H H 385 N NH CH₃ H CF₃ H H Cl 386 N NH CH₃ CH₃ 4-F—C₆H₄ H H CH₃ 387 N NH CH₃ H 2-F—C₆H₄ H P CO₂CH₃ 388 N NH CH₃ H 2-Cl—C₆H₄ H COCH₃ CO₂CH₃ 389 N NH CH₃ H 3-Cl—C₆H₄ H H CO₂CH₃ 390 N NH CH₃ H 4-Cl—C₆H₄ H H CO₂CH₃ 391 N NH CH₃ H CH₂Cl H CH₃ H 392 N NH CH₃ H CH₂Cl H CO₂C₂H₅ CF₃ 393 N NH CH₃ H CH₂Cl H H CF₃ 394 N NH CH₃ CH₃ M H CO₂C₂H₅ CF₃ 395 N NH CH₃ CH₃ CH₂Cl H H CF₃ 396 N NH CH₃ H CH₂Cl H H H 397 N NH CH₃ H CH₂Cl H H P 398 N NH CH₃ H CH₂Cl H P H 399 N NH CH₃ H CH₂Cl H COCH₃ H 400 N NH CH₃ CH₃ 3,5-diCl—C₆H₃ H CO₂CH₃ H 401 CH O H C₃H₇i CH₃ H H H oil 402 CH O H n-C₄H₉ CH₃ H H H 117–118 403 CH O H n-C₅H₁₁ CH₃ H H H 404 CH O H C₂H₄Pri CH₃ H H H oil 405 CH O H n-C₆H₁₃ CH₃ H H H 113–115 406 CH O H H n-C₄H₉ H H H 407 CH O H H n-C₅H₁₁ H H H 408 CH O H H CH(CH₃)₂ H H CH₃ 110–112 409 CH O H n-C₃H₇ n-C₃H₇ H H H 112–114 410 N O H Cl n-C₃H₇ H H H 136–138 411 N O H Cl C₆H₅ H H H 166–168 412 N O H n-C₃H₇ CH₃ H H H 121–122 413 N O H n-C₄H₉ CH₃ H H H 100–102 414 N O H n-C₆H₁₃ CH₃ H H H 75–78 415 CH O H CH₃ n-C₄H₉ H H H 416 CH O H C₂H₅ n-C₄H₉ H H H 417 CH O H C₃H₇ n-C₄H₉ H H H 418 CH O H i-C₃H₇ n-C₄H₉ H H H 419 CH O H n-C₄H₉ n-C₄H₉ H H H 420 CH O H CH₃ n-C₅H₁₁ H H H 421 CH O H C₂H₅ n-C₅H₁₁ H H H 422 CH O H C₃H₇ n-C₅H₁₁ H H H 423 CH O H i-C₃H₇ n-C₅H₁₁ H H H 424 CH O H n-C₄H₉ n-C₅H₁₁ H H H 425 CH O H H n-C₆H₁₃ H H H 426 CH O H CH₃ n-C₆H₁₃ H H H 427 CH O H C₂H₅ n-C₆H₁₃ H H H 428 CH O H C₃H₇ n-C₆H₁₃ H H H 429 CH O H i-C₃H₇ n-C₆H₁₃ H H H 430 CH O H n-C₄H₉ n-C₆H₁₃ H H H 431 N O H CH₃ n-C₄H₉ H H H 432 N O H C₂H₅ n-C₄H₉ H H H 433 N O H C₃H₇ n-C₄H₉ H H H 434 N O H i-C₃H₇ n-C₄H₉ H H H 435 N O H n-C₄H₉ n-C₄H₉ H H H 436 N O H CH₃ n-C₅H₁₁ H H H 437 N O H C₂H₅ n-C₅H₁₁ H H H 438 N O H C₃H₇ n-C₅H₁₁ H H H 439 N O H i-C₃H₇ n-C₅H₁₁ H H H 440 N O H n-C₄H₉ n-C₅H₁₁ H H H 441 N O H H n-C₆H₁₃ H H H 442 N O H CH₃ n-C₆H₁₃ H H H 443 N O H C₂H₅ n-C₆H₁₃ H H H 444 N O H C₃H₇ n-C₆H₁₃ H H H 445 N O H i-C₃H₇ n-C₆H₁₃ H H H 446 N O H n-C₄H₉ n-C₆H₁₃ H H H 447 N NH H CH₃ n-C₄H₉ H H H 448 N NH H C₂H₅ n-C₄H₉ H H H 449 N NH H C₃H₇ n-C₄H₉ H H H 450 N NH H i-C₃H₇ n-C₄H₉ H H H 451 N NH H n-C₄H₉ n-C₄H₉ H H H 452 N NH H CH₃ n-C₅H₁₁ H H H 453 N NH H C₂H₅ n-C₅H₁₁ H H H 454 N NH H C₃H₇ n-C₅H₁₁ H H H 455 N NH H i-C₃H₇ n-C₅H₁₁ H H H 456 N NH H n-C₄H₉ n-C₅H₁₁ H H H 457 N NH H H n-C₆H₁₃ H H H 458 N NH H CH₃ n-C₆H₁₃ H H H 459 N NH H C₂H₅ n-C₆H₁₃ H H H 460 N NH H C₃H₇ n-C₆H₁₃ H H H 461 N NH H i-C₃H₇ n-C₆H₁₃ H H H 462 N NH H n-C₄H₉ n-C₆H₁₃ H H H 463 CH O H H CH₂-Ph-4-Cl H H H 464 CH O H CH₃ CH₂-Ph-4-Cl H H H 465 CH O H C₂H₅ CH₂-Ph-4-Cl H H H 466 CH O H CH₂-Ph-4-Cl CH₃ H H H 467 CH O H CH₂-Ph-4-Cl C₂H₅ H H H 468 CH O H CH₂-Ph-4-Cl C₃H₇ H H H 469 CH O H CH₃ CF₃ H H H 470 CH O H Cl CF₃ H H H 471 CH O H C₂H₅ CF₃ H H H 472 CH O H n-C₃H₇ CF₃ H H H 473 CH O H n-C₄H₉ CF₃ H H H 474 CH O H H CH₂CH₂-Ph- H H H 4-Cl 475 CH O H CH₃ H H H 476 CH O H H CH₂Bu-t H H H 477 CH O H CH₃ CH₂Bu-t H H H 478 CH O H n-C₃H₇ CH₂Bu-t H H H 479 CH O H CH₂Bu-t CH₃ H H H 480 CH O H CH₂CH₂-Ph- CH₃ H H H 4-Cl 481 CH O H C₂H₅ H H H 482 CH O H C₃H₇ H H H 483 CH O H CO₂CH₃ CH₃ H H H 484 CH O H CO₂CH₃ CF₃ H H H 485 CH O H CO₂C₂H₅ C₂H₅ H H H 486 CH O H CO₂C₂H₅ n-C₃H₇ H H H 487 CH O H CONHCH₃ CH₃ H H H 488 CH O H CONHC₂H₅ CH₃ H H H 489 CH O H CON(CH₃)₂ CH₃ H H H 490 CH O H CH₃ CO₂CH₃ H H H *stands for melting point. ° C. is the unit.

The present invention also includes preparation of benzopyrone compounds and their isomers having general formula (I).

The compounds of formula I can be easily prepared by reaction of the benzylhalide having general formula (II) with benzopyrone compounds containing hydroxy group having general formula (III) under base condition according to the scheme I.

wherein: Z is leaving group, such as halogen (Cl, Br, or I).

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, A, B, is as defined above.

Preparation condition of compounds having general formula (I): In proper solvent, hydroxylbenzopyrone compounds having general formula (III) are treated with proper base to become salts, then the compound having general formula (II) is added into the mixture, the reaction is carried out at proper temperature. After reaction is completed, the target compound I is obtained by normal way.

The proper solvent mentioned may be selected from the following ones, such as tetrahydrofuran, acetonitrile, toluene, xylene, benzene, DMF, DMSO, acetone or butanone and so on.

The proper base mentioned may be selected from the following ones, such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, triethylamine, pyridine, pyridine or sodium hydride and so on.

The proper temperature mentioned is from room temperature to boiling point of solvent. Normal temperature is from 20 to 100° C.

The reaction may be finished in the course of 30 minutes-20 hours, generally 1-10 hours.

The reaction can be controlled by Thin-Layer Chromatography.

The intermediates of general formula (II) can be prepared according to the known methods, refer to U.S. Pat. No. 4,723,034 and U.S. Pat. No. 5,554,578.

Some of the hydroxylbenzopyrone compounds having general formula (III) are available from the chemical company, and are also prepared according to the methods reported in Journal of Medicinal Chemistry, 2001, 44 (5), 664-671, by the reaction R₅COCHR₄CO₂CH₃(C₂H₅) with substituted resorcinol. Moreover, the compound may be straightly used to prepare the target compounds without further purification. Some of the hydroxylbnezopyrone compounds having general formula (III) synthesized are showed in table 2.

TABLE 2 III R₄ R₅ R₆ R₇ R₈ Physical property* III-1 H CH₃ H H COCH₃ 158–160 III-2 H CH₃ H H C(═NOMe)CH₃ 129–140 III-3 H H₃ H H CO₂CH₃ 219–222 III-4 H CH₃ H H CH₃ 256–258 III-5 Cl CH₃ H H H 230–234 III-6 H CF₃ H H H 180–183 III-7 C₆H₅CH₂ CH₃ H H H 208–212 III-8 H 4-F—C₆H₄ H H H 256–262 III-9 H 3,4-(MeO)₂C₆H₄ H H H 184–188 III-10 F CH₃ H H H 203–206 III-11 H C₆H₅ H H H 240–242 III-12 H C₆H₅ H H CH₃ 260–262 III-13 Cl C₆H₅ H H H 188–190 III-14 CH₃ CH₃ H H H 118–120 III-15 CH₃ CH₃ H H CH₃ 218–222 III-16 H n-C₃H₇ H H CH₃ 176–178 III-17 Cl n-C₃H₇ H H H 148–150 III-18 H i-C₃H₇ H H H 160–162 III-19 n-C₆H₁₃ CH₃ H H H 170–172 III-20 i-C₃H₇CH₂CH₂ CH₃ H H H 101–102 III-21 n-C₄H₉ CH₃ H H H 134–136 III-22 n-C₃H₇ CH₃ H H H 142–144 III-23 H CH₂OCH₃ H H H 186–190 *stands for melting point. ° C. is the unit.

The compounds of general formula (V) and (VII) can be easily prepared by reaction of the general formula (IV) and (VI), respectively, with methylamine aqueous solution.

The present invention also provides a composition of insecticides and fungicides. The active ingredients of the composition are the compounds having general formula (I), wherein the active ones being present in a total amount of 0.1 to 99% by weight, the rest being the acceptable carrier by agriculture.

The present invention, further more, provides preparation method of the said composition thereon. The compounds of general formula (I) and the carrier are mixed. The said composition may be a single component compound or mixture of compounds with several components.

The carrier in the invention accords to the requirements: it is easy to apply to the sites being to be treated for the carrier after it is confected with active component. For example, the sites could be plant, seed or soil convenient for store, transport or operation. The carrier could be solid or liquid, including the liquid which usually turns from gas condition under pressure. And the carriers which are used to confect insecticidal, bactericidal composition are applied.

Suitable solid carriers include natural and synthetic clays and silicates, for example diatomaceous earths, talcs, magnesium aluminium silicates, aluminium silicates(kaolin), montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic silicon oxides and synthetic calcium silicates or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers or copolymers; solid polychlorophenols; bitumen; waxes, beeswax or paraffin wax for instance.

Suitable liquid carriers include water, alcohols such as isopropanol or alcohol; ketones such as acetone, methyl ethyl ketone, methyl isopropy ketone or cyclohexanone; ethers; aromatics such as benzene, xylene, toluene; petroleum fractions such as kerosene or mineral oils, chlorinated aliphatic hydrocarbons such as carbon tetrachloride, tetrachloride ethylene or trichloride ethylene. Mixtures of these different liquids generally are often suitable.

The compositions of insecticides and fungicides are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of surfactant facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surfactant. For example the composition may contain at least two carriers, at least one of which is, a surfactant.

A surfactant may be an emulsifier, a dispersant or a wetting agent; it may be nonionic or ionic. Examples of suitable surfactant include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycol, sorbic alcohol, sucrose or pentaerythritol and condensations of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols such as p-octylphenol or p-octylcresol, with ethylene-oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkaline metal salts or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as sodium dodecylbenzene sulphonate.

Examples of compositions and formulations according to the invention are wettable powder, Dustable powder, granule and aqueous solution; emulsifiable concentrate, emulsion, suspension concentrate, aerosol composition and fumigant. Wettable powder usually contains 25, 50 or 75% weight(ab.w) of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersant and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers. Dustable powder are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but a dispersant, and are diluted with further solid carrier to give a composition usually containing 0.5-10% weight of active ingredient. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules contain 0.5-75% w active ingredient and 0-10% weight of additives such as stabilisers, surfactants, slow release modifiers. The so-called “dry flowable powders” consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 1-50% weight /volume(ab. w/v) active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers.

Aqueous dispersant and emulsions, for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention. The said emulsions may be of the water-in-oil or of the oil-in-water type.

The composition to which one or more other fungicides are added has wider spectrum activity than single compound having general formula (I). In addition, other fungicides may have synergistic effect on the fungicidal activity of the compound having general formula (I). The compound having general formula (I) can also be used with other insecticides, or with another fungicide and other insecticides simultaneously.

This invention has the following advantages:

The compounds of present invention have very good insecticide activity, and may be used to control insects such as armyworm, diamond backmoth, aphids, carmine spider mite, two-spotted spider mite, lady beetles, mites and culex mosquitoes, especially for lady beetles and culex mosquitoes. All these attributes are suitable for integrated insect management.

The compounds of present invention have wide spectrum fungicidal activity, and may be used to control diseases in all sorts of plants caused by by oomycete, basidiomycete, ascomycete pathogens, and it may also provide good control efficacy at very low rate because of the high activity. These compounds have penetration activity and can be used as soil and foliar fungicides. They can provide satisfied control of grape downy mildew, rice sheath blight, rice blast, tomato early blight, tomato late blight, wheat leaf rust, wheat leaf blotch, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew and cucumber grey mold

DESCRIPTION OF THE INVENTION IN DETAIL

The following examples are illustrative of the present invention.

PREPARATION EXAMPLE Example 1 The Preparation of Compound 1

A reaction flask was charged a suspension of 60% sodium hydride 0.84 g (washed with petroleum ether), and then 30 ml of dry N,N-dimethylformamide (DMF) was added, the mixture was stirred at room temperature for 30 minutes. To this agitated suspension, 1.7 g of 7-hydroxycoumarin was added, the mixture was agitated continuously till to no gas emerging. 3.0 g of methyl (E)-α-[2-(bromomethyl)phenyl]-β-methoxyacrylate was added to the reaction mixture and they were agitated continuously for 3 hours at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate 3 times. The combined extracts were washed with brine 3 times, dried, filtered and concentrated under vacuum, to obtain the crude oil product 5 g. This was subjected to column chromatography to obtain 2.8 g of compound 1 as a faint red-yellow oily substance in 76.5% yield.

¹HNMR(300 MHz, internal standard=TMS, CDCl₃): δppm 3.69 (3H, s), 3.88 (3H, s), 5.04 (2H, s), 6.19-6.23 (1H, d), 6.77 (1H, s), 6.83-6.87 (1H, d), 7.18-7.20 (1H, m), 7.26-7.34 (4H, m), 7.48-7.64 (2H, m).

Example 2 The Preparation of Compound 2

A reaction flask was charged a suspension of 60% sodium hydride 0.45 g (washed with petroleum ether), and then 20 ml of dry N,N-dimethylformamide (DMF) was added, the mixture was stirred at room temperature for 30 minutes. To this agitated suspension, 1.0 g of 7-hydroxy-4-methylcoumarin was added, the mixture was agitated continuously till to no gas emerging. 1.66 g of methyl (E)-α-[2-(chloromethyl)phenyl]-β-methoxyacrylate was added to the reaction mixture and they were agitated continuously for 3 hours at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate 3 times. The combined extracts were washed with brine 3 times. Dried, filtered and concentrated, to obtain the crude product, as a yellow solid substance. This was subjected to column chromatography, using a 1:2 mixture of ethyl acetate and petroleum ether as the eluting solution to obtain 1.73 g of compound 2, with melting point of 140-143° C. in 80% yield.

¹HNMR(300 MHz, internal standard=TMS, CDCl₃): δppm 2.38 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.11 (1H, s), 6.77 (1H, s), 6.85-6.89 (1H, d), 7.17-7.20 (1H, m), 7.32-7.35 (2H, m), 7.49-7.52 (2H, m), 7.64 (1H, s).

Example 3 The Preparation of Compound 101

A reaction flask was added 1.2 g of K₂CO₃, 1.0 g of 7-hydroxy-4-methylcoumarin, 1.70 g of methyl (E)-2-(bromomethyl)-α-(methoxyimino)benzeneacetate and 20 ml Butanone, the reaction mixture was refluxed and agitated continuously for 5 hours. The reaction mixture was poured into ice water, extracted with ethyl acetate 3 times. The combined extracts were washed with brine 3 times, dried, filtered and concentrated under vacuum, to obtain the crude product, as a yellow solid substance. This was subjected to column chromatography, using a 1:2 mixture of ethyl acetate and petroleum ether as the eluting solution to obtain 1.77 g of compound 101, with melting point of 150-152° C. in 83% yield.

¹HNMR(300 MHz, internal standard=TMS, CDCl₃): δppm 2.39 (3H, s), 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.13 (1H, s), 6.80-6.86 (2H, m), 7.23-7.26 (1H, m), 7.43-7.49 (4H, m).

Example 4 The Preparation of Compound 153

A reaction flask was added 0.27 g of compound 101, more than two fold(mol)methylamine and 30 ml methanol, the reaction mixture was continuously agitated overnight, then concentrated and extracted with ethyl acetate 2 times. The combined extracts were washed with water 3 times and then washed with brine 2 times, dried, filtered and concentrated, to obtain 0.24 g of compound 153, with melting point of 210-214° C. in 89% yield.

¹HNMR(300 MHz, internal standard=TMS, CDCl₃): δppm 2.38 (3H, s), 2.91-2.93 (3H, d), 3.97 (3H, s), 5.02 (2H, s), 6.13 (1H, s), 6.82-6.87 (3H, m), 7.23 (1H, d), 7.39-7.50 (4H, m).

The preparation of other compounds, please refers to the way as above. ¹HNMR of other compounds are provided as follows (300 MHz, internal standard=TMS, CDCl₃):

Compound 3: δppm 2.36 (3H, s), 2.37 (3H, s), 3.72 (3H, s), 3.84 (3H, s), 5.09 (2H, s), 6.13 (1H, s), 6.75-6.78 (1H, d), 7.18-7.21 (1H, m), 7.34-7.36 (3H, m), 7.50-7.52 (1H, m)7.61 (1H, s).

Compound 4: δppm 2.41 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.08 (2H, s), 6.20 (1H, s), 6.68-6.71 (1H, d), 7.18-7.21 (4H, m), 7.32-7.50 (5H, m), 7.59 (1H, s), 7.92 (1H, m).

Compound 5: δppm 2.17 (3H, s), 2.35 (3H, s), 3.73 (3H, s), 3.88 (3H, s), 5.02 (2H, s), 6.78 (1H, s), 6.83-6.85 (1H, d), 7.31-7.34 (3H, m), 7.45-7.47 (2H, d), 7.62 (1H, s).

Compound 6: δppm 2.32 (3H, s), 2.31-2.36 (6H, d), 3.69 (3H, s), 3.84 (3H, s), 5.07 (2H, s), 6.74-6.77 (1H, d), 7.17-7.20 (1H, m), 7.31-7.36 (3H, m), 7.51-7.54 (1H, m), 7.61 (1H, s).

Compound 12: δppm 2.53 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, s), 6.83-6.85 (1H, d), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.47-7.50 (2H, d), 7.64 (1H, s).

Compound 17: δppm 1.25-1.32 (3H, m), 2.36 (3H, s), 2.74-2.76 (2H, m), 3.71 (3H, s), 3.84 (3H, s), 5.08 (2H, s), 6.15 (1H, s), 6.75-6.78 (1H, d), 7.18-7.21 (1H, m), 7.33-7.38 (3H, m), 7.50-7.54 (1H, m), 7.61 (1H, s).

Compound 18: δppm 1.10-1.15 (3H, t), 2.37 (3H, s), 2.60-2.68 (2H, q), 3.74 (3H, s), 3.89 (3H, s), 5.03 (2H, s), 6.76 (1H, d), 6.84-6.88 (1H, dd), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.45-7.53 (2H, m), 7.63 (1H, s).

Compound 19: δppm 3.48 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 4.56 (2H, s), 5.04 (2H, s), 6.34 (1H, s), 6.79 (1H, d), 6.84-6.88 (1H, dd), 7.18-7.21 (1H, m), 7.30-7.36 (2H, m), 7.41-7.44 (1H, d), 7.48-7.51 (1H, m), 7.64 (1H, s).

Compound 24: δppm 3.72 (3H, s), 3.92 (3H, s), 5.10 (2H, s), 6.78 (1H, s), 6.94-7.21 (1H, d), 7.22 (1H, m), 7.33-7.35 (2H, m), 7.36-7.45 (2H, m), 7.66 (1H, s), 8.13 (1H, s).

Compound 25: δppm 2.36 (3H, d), 2.62 (3H, d), 3.71 (3H, s), 3.84 (3H, s), 5.09 (2H, s), 6.82 (1H, d), 7.19-7.21 (1H, m), 7.33-7.35 (3H, m), 7.36-7.37 (1H, m), 7.61 (1H, s).

Compound 26: δppm 1.25-1.30 (6H, m), 3.20-3.23 (1H, m), 3.74 (3H, s), 3.91 (3H, s), 5.04 (2H, s), 6.15 (1H, s), 6.790-6.799 (1H, d), 6.80-6.90 (1H, m), 7.18-7.23 (1H, m), 7.32-7.37 (2H, m), 7.48-7.57 (2H, m), 7.64 (1H, s).

Compound 27: 8ppm 0.95-1.00 (3H, t), 1.58 (2H, m), 2.36 (3H, s), 2.58 (2H, t), 3.73 (3H, s), 3.89 (3H, s), 5.02 (2H, s), 6.75 (1H, d), 6.84-6.88 (1H, dd), -7.18 (1H, m), 7.31-7.34 (1H, m), 7.47-7.51 (2H, m), 7.63 (1H, s).

Compound 29: δppm 3.74 (3H, s), 3.90 (3H, s), 5.06 (2H, s, ), 6.17 (1H, s), 6.80-6.85 (2H, m), 7.24-7.26 (1H, m), 7.28-7.35 (5H, m), 7.38-7.51 (3H, m), 7.66 (1H, s).

Compound 32: δppm 3.73 (3H, s), 3.90 (3H, s), 5.05 (2H, s), 6.75-6.78 (1H, dd), 6.84-6.85 (1H, d), 6.94-6.98 (1H, d), 7.19-7.21 (1H, m), 7.30-7.35 (4H, m), 7.53-7.55 (4H, m), 7.65 (1H, s).

Compound 33: δppm 1.27-1.32 (3H, m), 2.74-2.77 (2H, m), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.13 (1H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, m), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.48-7.52 (2H, m), 7.64 (1H, s).

Compound 34: δppm 0.90-1.03 (3H, m), 1.67-1.72 (2H, m), 2.65-2.70 (2H, m), 3.73 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.10 (1H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, m), 7.19-7.21 (1H, m), 7.33-7.35 (2H, m), 7.47-7.51 (2H, m), 7.64 (1H, s).

Compound 35: δppm 1.00-1.25 (3H, m), 1.69-1.72 (2H, m), 2.36 (3H, s), 2.65-2.70 (2H, m), 3.71 (3H, s), 3.84 (3H, s), 5.08 (2H, s), 6.12 (1H, s), 6.75-6.78 (1H, d), 7.21-7.26 (1H, m), 7.33-7.38 (3H, m), 7.50-7.53 (1H, m), 7.61 (1H, s).

Compound 36: δppm 0.97 (3H, t), 1.66 (2H, m), 2.67 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.85-6.88 (1H, dd), 7.22 (1H, m), 7.33-7.35 (2H, m), 7.46-7.49 (2H, m), 7.64 (1H, s).

Compound 37: δppm 1.05 (3H, m), 1.57-1.64 (2H, m), 2.16 (3H, s), 2.71-2.76 (2H, t), 3.70 (3H, s), 3.83 (3H, s), 5.02 (2H, s), 6.78 (1H, d), 6.87 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.45 (2H, m), 7.64 (1H, s).

Compound 38: δppm(DMSO-d₆) 3.65 (3H, s), 3.88 (3H, s), 5.03 (2H, s), -6.15 (1H, s), 6.83-6.87 (1H, dd), 6.91 (1H, d), 7.09-7.17 (2H, m), 7.23-7.35 (4H, m), 7.43-7.46 (1H, m), 7.51-7.55 (2H, m), 7.66 (1H, s).

Compound 41: δppm 3.74 (3H, s), 3.91 (3H, s), 5.06 (2H, s), 6.20 (1H, s), 6.86 (2H, m), 7.22 (2H, m), 7.33-7.36 (2H, m), 7.56 (3H, m), 7.66 (1H, s), 7.77 (2H, d). Compound 50: δppm 2.34 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78-6.79 (1H, d), 6.92-6.96 (1H, dd), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.41-7.44 (1H, d), 7.48-7.51 (1H, m), 7.65 (1H, s).

Compound 52: δppm 3.74 (3H, s), 3.90 (3H, s), 5.06 (2H, s), 6.20 (1H, s), 6.80-6.86 (1H, m), 7.18-7.22 (1H, m), 7.32-7.37 (4H, m), 7.41-7.44 (2H, m), 7.50-7.52 (4H, m), 7.65 (1H, s).

Compound 58: δppm 3.74 (3H, s), 3.91 (6H, d), 3.96 (3H, s), 5.06 (2H, s), 6.19 (1H, s), 6.81-6.82 (1H, m), .6.85 (1H, s), 6.93-7.04 (3H, m), 7.19-7.22 (1H, m), 7.33-7.36 (2H, m), 7.44-7.52 (2H, m), 7.66 (11H, s).

Compound 68: δppm(DMSO-d₆) 2.49 (3H, s), 3.66 (3H, s), 3.89 (3H, s), 3.92 (2H, s), 5.00 (2H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, dd), 7.10-7.22 (6H, m), 7.26-7.29 (2H, m), 7.42 (1H, m), 7.61-7.66 (2H, m).

Compound 100: 8ppm 2.54 (3H, s), 3.87 (3H, s), 4.04 (3H, s), 5.02 (2H, s), 6.81-6.85 (1H, s), 7.26 (1H, d), 7.43-7.52 (5H, m).

Compound 102: δppm 2.32 (3H, s), 2.37 (3H, s), 3.84 (3H, s), 4.03 (3H, s), 5.05 (2H, s), 6.13 (1H, s), 6.76-6.79 (1H, d), 7.26 (1H, d), 7.34-7.43 (3H, m), 7.45-7.46 (1H, d).

Compound 103: δppm 2.18 (3H, s), 2.37 (3H, s), 3.91 (3H, s), 3.98 (3H, s), 5.35 (2H, s), 6.85 (1H, s), 6. 86-6.88 (1H, d), 7.26-7.40 (3H, m), 7.49-7.52 (1H, d), 7.62-7.65 (1H, d).

Compound 104: δppm 2.17 (3H, s), 2.35 (3H, s), 3.86 (3H, s), 4.04 (3H, s), 5.00 (2H, s), 6.78-6.85 (2H, m), 7.20-7.25 (1H, d), 7.40-7.61 (4H, m).

Compound 109: δppm 2.91-2.93 (3H, d), 3.97 (3H, s), 5.02 (2H, s), 6.23-6.26 (1H, d), 6.82-6.86 (3H, m), 7.20-7.23 (1H, m), 7.34-7.37 (1H, d), 7.39-7.45 (2H, m), 7.50-7.53 (1H, m), 7.61-7.64 (1H, d).

Compound 111: 8ppm 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.23-6.26 (1H, d), 6.79-6.85 (2H, m), 7.21 (1H, d), 7.34-7.37 (1H, d), 7.41-7.45 (2H, m), 7.47-7.53 (1H, m), 7.61-7.64 (1H, d).

Compound 401: δppm 1.32-1.36 (6H, m), 2.39 (3H, s), 3.27 (1H, m), 3.74 (3H, s), 3.89 (3H, s), 5.03 (2H, s), 6.72-6.73 (1H, d), 6.83-6.87 (1H, dd), 7.17-7.20 (1H, m), 7.31-7.34 (2H, m), 7.46-7.52 (2H, m), 7.63 (1H, s).

Compound 402: δppm 0.93 (3H, m), 1.45 (4H, m), 2.35 (3H, s), 2.60 (2H, t), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.84-6.85 (1H, m), 7.18-7.20 (1H, m), 7.30-7.35 (2H, m), 7.45-7.50 (2H, d), 7.64 (1H, s).

Compound 404: δppm 1.25 (6H, m), 1.39 (2H, m), 1.63 (1H, m), 2.39 (3H, s), 2.62 (2H, t), 3.72 (3H, s), 3.86 (3H, s), 5.01 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.45 (2H, d), 7.64 (1H, s).

Compound 405: δppm 0.88 (3H, t), 1.42-1.52 (8H, m), 2.38 (3H, s), 2.64 (2H, t), 3.72 (3H, s), 3.86 (3H, s), 5.01 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.45 (2H, d), 7.64 (1H, s).

Compound 408: 8ppm 2.37 (3H, s), 3.2-3.6 (1H, m), 3.72 (3H, s), 3.85 (3H, s), 5.09 (2H, s), 6.18 (1H, s), 6.76-6.79 (1H, d), 7.18-7.21 (1H, m), 7.34-7.43 (3H, m), 7.51-7.54 (1H, m), 7.68 (1H, 5).

Compound 409: δppm 0.96-1.03 (6H, m), 1.58-1.63 (4H, m), 2.71-2.79 (4H, m), 3.72 (3H, s), 3.85 (3H, s), 5.00 (2H, s), 6.79 (1H, d), 6.87 (1H, m), 7.19 (1H, m), 7.32 (2H, m), 7.45 (2H, m), 7.64 (1H, s).

Compound 410: 8ppm 0.86-0.88 (3H, m), 1.68-1.75 (2H, m), 2.66-2.71 (2H, m), 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.80-6.92 (3H, m), 7.21-7.26 (1H, d), 7.39-7.69 (3H, m).

Compound 411: δppm 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.73-6.77 (1H, m), 6.87-6.88 (1H, d), 6.97-7.00 (1H, d), 7.21-7.24 (1H, m), 7.28-7.32 (2H, m), 7.42-7.57 (6H, m).

Compound 412: δppm 0.94 (3H, t), 1.46 (2H, m), 2.35 (3H, s), 2.60 (2H, t), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.42-7.45 (2H, d), 7.64 (1H, s).

Compound 413: δppm 0.94 (3H, m), 1.45 (4H, m), 2.36 (3H, s), 2.60 (2H, t), 3.86 (3H, s), 4.05 (3H, s), 5.00 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.38-7.45 (4H, m).

Compound 414: δppm 0.88 (3H, m), 1.48-1.65 (8H, m), 2.36 (3H, s), 2.62 (2H, t), 3.86 (3H, s), 4.05 (3H, s), 5.00 (2H,.s), 6.85 (1H, m), 6.84 (1H, m), 7.20 (1H, m), 7.39-7.45 (4H, m).

Formulation Example (Weight/Weight %) Example 5 60% Wettable Powder

Compound 6 60%  Sodium dodecylnaphthalenesulfate 2% Sodium lignosulphonate 9% Kaolin complement to 100%

All the solid components are well mixed and shattered until the particle size of the active ingredient reaches the standard in order to obtain 60% wettable powder.

Example 6 35% Emulsion Concentrate

Compound 1 35% Phosphorous acid 10% Ethylenoxy aliphatic acid glycerin ester 15% Cyclohexanone complement to 100%

Phosphorous acid is dissolved in cyclohexanone, then the compound 1 and ethylenoxy aliphatic acid glycerin ester are added, a emulsifiable concentrate in transparent solution is obtained finally.

Example 7 30% Aqueous Suspension Concentrate

Compound 25 30%  Sodium dodecylnaphthalenesulfate 4% Hemicellulose 2% Epoxypropane 8% Water complement to 100%

The mixture of compound 25, 80% of the amount of water should being added and sodium dodecylnaphthalenesulfate are shattered in a mill (1 mm ball). Other components are dissolved in the rest water, and are added under stirring.

Example 8 25% Suspension Emulsifier

Compound 12  25% Alkylsulphonates (emulsifier 1)   4% Ethylenoxy aliphatic acid glycerin ester   2% (emulsifier 2) Calcium dodecylbenzenesulfate (emulsifier 3) 1.5% Polyethylenoxyalkyl propyl ether (dispersant) 2.5% Cyclohexanone (solvent 1)  30% Petroleum fractions (boiling point >200° C.) complement to 100% (solvent 2)

Compound 12 is dissolved in 80% of the amount of solvent should being added, and then emulsifiers and dispersant are added, the mixture is stirred completely and shattered in a mill(1 mm ball). Other solvents are added.

Test of Biological Activity

Example 9 Fungicidal Activity Determination

Determination of fungicidal activities against plant diseases of selected compounds were carried out by following procedure:

Plants were prepared in pot. Technical samples were dissolved in DMF and diluted to required concentration by water. Test solution was sprayed onto potted plant. Pathogen inoculation was carried out after 24 hours then plants were hold in growth chambers containing constant temperature and moisture for effect. When untreated plant was under desirable disease severity (after 1 week approximately), assessment was carried out by visual observation.

Part of test results:

At 200 ppm, compound 1, 2, 4, 5, 6, 12, 18, 19, 25, 26, 33, 34, 35, 37, 50, 52, 58, 69, 109, 402, 405, 409, 410, 413, 414 showed 100% control against cucumber downy mildew, while compound 3, 24, 36, 38, 153, 411 showed >95% control.

At 200 ppm, compound 2, 6, 18, 50, 58, 100, 402 showed 100% control against cucumber grey mold, while 6, 101, 102, 103, 106, 412 showed >75% control.

At 200 ppm, compound 6, 7, 10 showed 100% against grape downy mildew, while 8, 106, 154 showed >85% control.

At 200 ppm, compound 3, 101 showed >85% control against rice sheath blight.

At 200 ppm, compound 6, 8, 10 showed >85% control against rice blast.

At 200 ppm, compound 402, 412, 413 showed 100% control against wheat powdery mildew, while 9, 101, 111, 410 showed >70% control.

At 200 ppm, compound 6 showed 100% control against wheat leaf rust, while 7, 10 showed >95% control and 8, 154 showed >75% control.

At 200 ppm, compound 6>90% and compound 7, 8, 9, 10, 11, 154 showed >80% control against wheat leaf blotch.

At 200 ppm, compound 6, 7 showed >100% control against tomato early stage blight, while 8, 10 showed >90% control, while 11 showed >75% control.

At 200 ppm, compound 6 showed >95% control against tomato late blight, while 10 showed >75% control.

At 200 ppm, compound 5, 6 showed >95% control against corn leaf blight. Comparing with the compound JP51 in JP04-182461, the part of test results of some compounds activity against cucumber downy mildew refers to table 3.

TABLE 3 Comparision of fungicidal activity against cucumber downy mildew (50 ppm) Compound 1 2 5 6 12 26 37 52 402 405 409 141 JP51 control(%) 100 100 100 100 100 100 100 100 100 100 100 100 20

Example 10 Determination of Insecticidal/Acaricidal Activity

Numerous insect larvae were put into containers then were fed with treated corn leaves. Potter's spraying tower was used as the sprayer and spraying volume was 1 mL. The spraying pressure was 13.5 lb/in².

Test Result:

At 10 ppm, compound 2, 5, 6 showed 100% control of culex mosquitoes. At 600 ppm, compound 5 and 6 showed >50% control of army worm, diamond backmoth and green peach aphid.

At 300 ppm, compound 7, 9, 10 showed 100% control of Mexican lady beetle, while compound 7 showed >50% control of two-spotted spider mite. 

1. A benzopyrone compound having the general formula (I):

wherein: A is CH; B is O; R₁, R₂, and R₅ are methyl; R₃, R₆, R₇, and R₈ are H; R₄ is methyl or n-butyl.
 2. A method of controlling insects which comprises applying the compound according to claim 1 to a plant.
 3. A method of controlling fungi which comprises applying the compound according to claim 1 to a plant.
 4. A fungicidal or insecticidal composition comprising the compound of claim 1 as an active ingredient, wherein the weight percentage of the active ingredient in the composition is from 0.1 to 99%. 